Study of polycarbonate–polystyrene interfaces using scanning transmission electron microscopy spectrum imaging (STEM-SI)

Polymer blends are important for both commercial utility and scientific understanding. The degree of interfacial mixing in polymer blends is important since it influences the blends' mechanical properties. Understanding bulk properties in multiphase polymeric materials requires knowledge of the interfacial properties of the materials. The characterization of the interface, in terms of its width and composition profile, provides insight about the bulk behaviour of the material. Chemical microscopy through electron energy-loss spectroscopy (EELS) in a transmission electron microscope is gaining popularity to characterize narrow polymer–polymer interfaces. In this work, we show how scanning transmission electron microscopy spectrum imaging, a spatially resolved energy-loss spectroscopy, can be employed to calculate the interfacial width in a pair of immiscible polymers, taking a polycarbonate–polystyrene (PC-PS) bilayer as an example. By mapping peaks unique to each of the blend constituents at several points across the interface, we show how the interfacial profile concentrations can be determined. With this method we calculated the interfacial width in the PC-PS bilayer sample to be approximately 32 nm, even utilizing low resolution spectrometers, which are more widely available. Using the technique described with higher resolution EELS instruments having a better signal-to-noise ratio, a higher spatial resolution can be achieved. Using EELS chemical fingerprints of polymers that have been developed earlier, the technique presented here has the potential for effective visualization and morphological measurements of phase-differentiated polymer blends. This paper is an attempt to enable a new user to characterize polymer–polymer interfaces using chemical microscopy. © 2022 Society of Industrial Chemistry.     

Influence of hydrogen peroxide-based bleaching agents on the bond strength of resin–enamel/dentin interfaces

This study evaluated the effect of different bleaching techniques on the bond strength of pre-existing adhesive restorations in enamel and dentin. Hydrogen peroxide-based bleaching gels with different concentrations (7.5% and 35%) were used on composite restorations of Adper Single Bond 2 (3M/ESPE, St. Paul, USA) and Filtek Z250 (3M/ESPE, St. Paul, USA). Twenty human third molars were randomly divided into 8 groups: GE—enamel control; GE7.5—bleaching using 7.5% hydrogen peroxide; GE35—bleaching using 35% hydrogen peroxide; GE 7.5+35—bleaching using 7.5% and 35% hydrogen peroxide; GD—dentin control; GD7.5—7.5% hydrogen peroxide; GD35—35% hydrogen peroxide; and GD 7.5+35—7.5% and 35% hydrogen peroxide. Bleaching was performed using long clinical application-time to low concentration gel, and short clinical application-time to high concentration gel. Unbleached specimens were stored in artificial saliva for 14 days. Specimens subject to micro-shear testing and data were analyzed by Analysis of Variance and Tukey's test (p=0.05). Enamel micro-shear bond strength was reduced after 7.5% hydrogen peroxide and after association of 7.5% and 35% hydrogen peroxide. Bleaching treatment altered dentin bond strength only when using 7.5% hydrogen peroxide. The results suggest that the bond strength of the restorations was influenced by the clinical extent of bleaching-gel application time and was not dependent on bleaching-gel concentration.     

A kinetic study of the isothermal degradation process of Lexan® using the conventional and Weibull kinetic analysis

The degradation process of commercial grade Lexan® was investigated by thermogravimetric technique under isothermal experimental conditions at four different operating temperatures: 375 °C, 387.5 °C, 400 °C and 425 °C. The kinetic triplet (E _a , A, f(α)) was determined using conventional and Weibull kinetic analysis. The applied kinetic procedure shows that the investigated degradation process can be described by two-parameter autocatalytic ?esták–Berggren (SB) reaction model. It was established that the degradation process of Lexan® can be described by the following kinetic triplet: E _a? =?158.3 kJ mol^?1, A?=?8.80?×?10⁹ min^?1 and f(α)?=?α ^0.33 (1???α)^1.62. It was established that the operating temperature has an influence on the values of SB reaction orders (m and n) (0.27?m?n??1, represent the composite value from a complex degradation reaction and can not compare with the dissociation energy of the weak bonds in bisphenol-A polycarbonate. Also, it was concluded that the Weibull shape parameter (β) shows that the considered process occurs under the same reaction mechanism, independently on operating temperature (T), i.e. the change of rate-limiting step does not occur (β?ddf) of apparent activation energies for considered degradation process. On the other hand, it was shown that the experimentally evaluated density distribution function of apparent activation energies represents the intermediate case between the calculated density distribution functions at 375 °C and 425 °C.     

Combined application of 13C NMR spectroscopy and confocal laser scanning microscopy—Investigation on biofilm structure and physico-chemical properties

Long-term biofilm processes are influenced by the interplay of biofilm accumulation and detachment, which in turn depend partially on the biofilm structure and composition. In this study a combination of confocal laser scanning microscopy (CLSM) and nuclear magnetic resonance (NMR) spectroscopy was applied to analyze biofilm structure, composition and molecular mobility. Whereas CLSM delivers information about the structure of biofilms the NMR measurement provides detailed but not locally resolved information about the chemical composition of biofilm constituents. Heterotrophic mixed-species biofilms were cultivated in rotating annular reactors exposed to different flow conditions and glucose concentrations in order to obtain biofilms with diverse architectural structures. The growth state of the biofilms appeared to influence the composition of biofilm and detached biomass. The difference in the ¹³C NMR spectra between the differently structured biofilms or between biofilm and detached biomass was small, except for the still exponential growing biofilm supplied with the highest glucose concentration. More information was gained from the mobility of specific molecular groups within the biofilm biomass. Molecules within the biofilm biomass of the non-filamentous biofilms were more strongly bound than the molecules within the respective detached biomass. Glucose starvation resulted in a reduction in the biofilm molecular mobility. The opposite was observed in the filamentous biofilm. In this case, the molecular mobility in the biofilm increased after starvation and the molecules in the detached biomass were bound more strongly than in the respective biofilm biomass. It could be shown that the combination of CLSM and ¹³C NMR spectroscopy is a promising approach to analyze the interactions between biofilm architecture, composition or growth state and biofilm detachment.     

Preparation and properties of bisphenol A epoxy resin microcapsules coated with melamine–formaldehyde resin

Microcapsules containing epoxy resins have potential applications, such as in adhesive, electronic packaging, and self-healing polymeric composites. A series of microcapsules were prepared by in situ polymerization with poly(melamine–formaldehyde) as the shell materials and a mixture of diglycidyl ether of bisphenol A and epoxy diluent as the core substances. Morphology, chemical structure, mean particle size, and thermal properties of the microcapsules were studied by means of optical microscope, Fourier transform infrared spectroscopy, laser particle size analyzer, and microcomputer differential thermal balance, respectively. Effects of kind of epoxy diluent, surfactant type, emulsifier concentration, and emulsifying rate on the physical properties of microcapsules were investigated. Results indicate that the formation of microcapsules is affected by the epoxy diluent type and surfactant type. The highest core content of the resultant microcapsules is about 88 wt% and average diameters of the capsules range from 67 to 201 μm, which can be adjusted by changing the emulsifier concentration and emulsifying rate. Thermo gravimetric analysis indicated that the prepared microcapsules experienced excellent stability up to 235 °C.     

Influence of silver on electrochemical and corrosion behaviours of Pb–Ca–Sn–Al grid alloys Part II: A.c. impedance and scanning electron microscopy studies

The influence of silver, in the range of 0.02 to 0.07wt%, on the electrochemical and corrosion properties of Pb–Ca–Sn–Al grid alloy in sulphuric acid solutions at room temperature was investigated by electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). EIS was used to study the effect of silver on the surface layer(s) of an electrode under different conditions, while the oxide layers produced on the working electrode surface were examined by SEM. The addition of silver in the alloy inhibits the reactions of Pb to PbSO4 and PbSO4 to PbO2 and produces a more dense oxide layer which could enhance the corrosion resistance of the alloy.     

Identification and quantification of reaction phases at Si3N4–Ti interfaces by using analytical transmission electron microscopy techniques

Silicon nitride (Si₃N₄) and titanium (Ti) were successfully bonded by using a capacitor discharge joining method. The resulting sample interfaces were characterized by scanning electron microscopy (SEM) and analytical transmission electron microscopy (TEM) techniques. SEM and chemical analyses by energy dispersive X-ray spectrometry (EDX) and wave length X-ray spectrometry (WDX) showed that if there is a reaction layer it is very small. Sample preparation from metal–ceramic joints for TEM by using conventional techniques is difficult. To overcome this problem, samples were prepared by using a focus ion beam (FIB) and investigated by TEM techniques. Analytical TEM techniques such as electron energy loss spectroscopy (EELS) revealed that Si₃N₄ interacted with Ti and reaction phases were formed at the interface. These phases are approximately 50 nm thick Ti₃N₂ layer at the interface next to Si₃N₄ followed by continuous Ti₆Si₃N phase as a matrix containing Ti₃N particles.     

Mechanism of MgO dissolution in MgF2–CaF2–MF (M=Li or Na) melts: Kinetic analysis via in-situ high temperature confocal scanning laser microscopy (HT-CSLM)

The solid oxide membrane (SOM) process is a direct electrolysis method for refining magnesium and has become a popular and promising technology. In the electrolysis process of SOM, the metal oxide is dissociated into the metal cation and oxygen anion. Thus, it is important to investigate the dissolution reaction of metal oxides in molten fluoride flux, which contributes to the overall reaction mechanism and reaction rate. However, there are few fundamental studies on the reaction between oxide particles and fluoride flux. Notably, the dissolution behavior of magnesium oxide (MgO), which is a major source of magnesium production, into fluoride flux has not been reported. In addition, the dissolution behavior is mediated by the chemical and physical properties of the flux. Therefore, we investigated the dissolution reaction of MgO in fluoride flux using high temperature confocal scanning laser microscopy (HT-CSLM) measurements to demonstrate the reaction mechanism governing the dissolution rate of MgO particles. Consequently, the rate-limiting mechanism is a diffusion of O²⁻ ion, dissociated from MgO, through the boundary layer.     

Investigation of hot pressed ZrB2–SiC–carbon black nanocomposite by scanning and transmission electron microscopy

Hybrid ZrB₂-based composite having 10 vol% nano-sized carbon black and 20 vol% SiC was fabricated by vacuum hot pressing at 1850 °C under 20 MPa for 60 min. The microstructure and sinterability of the as-sintered ceramic was studied by X-ray powder diffraction, scanning electron microscopy, X-ray spectroscopy, scanning transmission electron microscopy and transmission electron microscopy analyses. A fully-dense hybrid composite could be achieved by hot pressing method under the aforementioned conditions. No new in-situ phase formation was detected after sintering process. Although the densification progressed in a non-reactive manner, the addition of carbonaceous material assisted the sinterability acting as the surface oxides cleaner. The precise phase and nanostructural investigations of the prepared ceramic verified the partial graphitization of carbon black and conversion of amorphous nano-additive into crystalline graphite nano-flakes.     

Microscopic evaluation of the thickness and structure of the cement and cement–dentin interdiffusion zone after luting posts with three different luting cements

Clinical studies report that failures of fiber post cementation occur mainly at the cement–dentin interface. The aim of this in vitro study is to compare the scanning electron microscopic (SEM) evaluations of the cement thicknesses in the root canals and the thickness of cement–dentin interface zones obtained after luting standardized glass-fiber posts with three different types of luting cements. Thirty single-rooted mandibular premolars of similar sizes were prepared for post insertion after biomechanical preparation and obturation. They were divided into three groups containing 10 samples each. Standardized glass-fiber posts were cemented with zinc phosphate cement for ZNP group, with conventional adhesive resin cement for CAR group, and with self-adhesive resin cement for SAR group. The formation and thickness of cement and cement–dentin interface zone were evaluated by stereomicroscope and SEM using ×800 magnification, and the data were analyzed. There was no significant difference between groups in terms of cement thickness (p = 0.835); however, there were significant differences among the cement layer thicknesses measured at the three examined levels of the root canals (p = 0.000). The groups using conventional adhesive resin cement presented longer micromechanical interlocking while the groups using self-adhesive resin cement showed wide gaps and zinc phosphate cement showed no bonding between cement–dentin interdiffusion zones along the root canal. As a clinical consequence, the use of zinc phosphate cement may not provide strong bond between dentin–cement interface. Conventional adhesive resin cements showed reliable bond to dentin when compared to zinc phosphate and self-adhesive resin cement.     

Equilibrium,kinetics and thermodynamic studies for the removal of organophosphorus pesticide using Amberlyst-15 resin: Quantitative analysis by liquid chromatography–mass spectrometry

In the present paper, Amberlyst-15 resin was used for the removal of malathion. Various experimental parameters such as effect of pH, contact time, resin dose, initial malathion concentration and temperature were studied to find the optimum conditions for malathion removal. The removal rate of malathion by Amberlyst-15 was rapid and equilibrium was established within 30 min. Kinetic studies showed better applicability for pseudo-second-order model and equilibrium data was best fitted to Freundlich isotherm model. The thermodynamic parameters showed that the adsorption of malathion was feasible, endothermic and spontaneous. The concentration of malathion was determined using ultra-performance liquid chromatography–tandem mass spectrometry.     

Carbon reactivity of binder metals in diamond–metal composites – characterization by scanning electron microscopy and X-ray diffraction

Diamond tooling is a successfully used technique in machining of very hard materials such as minerals and concrete. The type and strength of bonding between the diamond grains, that are mainly responsible for the machining process (e.g. cutting or grinding), and the metallic binder phase is directly linked to the tools quality. Therefore it is of interest to investigate the carbon reactivity of commonly used binder materials.This paper reports about the investigation of the interfacial area between diamonds and one-component metallic binder matrices. As matrix material pure chromium, cobalt, copper, iron, and nickel was used. After the sintering process the diamonds were extracted from the metallic matrix and analyzed by scanning electron microscopy and X-ray diffraction. The morphology of the diamond surface was investigated and a phase analysis was done. These experimental studies support the hypothesis that the carbon reactivity of transition metals is linked to their d-orbital electron configuration.     

Research on selective laser sintering of Kaolin–epoxy resin ceramic powders combined with cold isostatic pressing and sintering

In order to fabricate traditional products with complex shapes consisting of Kaolin ceramic, selective laser sintering (SLS) combined with cold isostatic pressing (CIP) process was used to consolidate Kaolin powder with additive of epoxy resin E06. To begin preparing the material, epoxy resin (10 wt%) and Kaolin were combined through mechanical mixing, which provided a good fluidity for SLS. Investigations on the shrinkage and micro topography of Kaolin–epoxy resin SLS samples were conducted to optimize the laser sintering parameters. It was found that SLS samples represented acceptable shrinkage and high density when laser energy density was 0.3300–0.3763 J/mm². Then the SLS samples were processed by CIP to eliminate the pores in green ceramics. Finally, the optimized SLS/CIP Kaolin samples were debinded and sintered to produce crack-free Kaolin ceramics. The “Yellow Duck” Kaolin ceramic product was fabricated by combining SLS/CIP with colored glazing. The study shows a novel and promising approach to fabricate complex traditional ceramic products via SLS combined with CIP and sintering.     

In-situ monitoring of pharmaceutical and specialty chemicals crystallization processes using endoscopy–stroboscopy and multivariate image analysis

This contribution presents the proof of concept of endoscopy–stroboscopy based in situ low-cost imaging of crystallization processes. This low-cost sensor currently is widely spread in the field of medical diagnosis of human vocal chords and this work presents its application in the context of pharmaceutical and chemical crystallization process monitoring. The model compounds used in this study are the active pharmaceutical ingredient (API) flufenamic acid and citric acid.     

A novel B–Si–Zr hybridized ceramizable phenolic resin and the thermal insulation properties of its fiber-reinforced composites

A novel B–Si–Zr hybridized ceramicizable resin(BSZ-PR) was fabricated by chemical reaction of boric acid, zirconium hydroxyl-containing polyhedral oligomeric silsesquioxane(Zr-POSS) and phenolic. The incorporation of boric acid and Zr-POSS improved the thermal stability of the resin effectively, and the residual carbon rate increased to 72.63% at 800 °C under nitrogen atmosphere. The flexural strength of carbon fiber/BSZ-PR and high silica fiber/BSZ-PR composites were increased by 25.7% and 175.5%, and linear ablation rates were reduced by 37% and 44.75%, respectively. It was discovered that the ceramic structures such as SiO₂, ZrO₂ and SiC can be formed at high temperatures as well as under extreme ablative conditions from both BSZ-PR and its fiber-reinforced composites, which may be the key to the improved thermal, ablative properties.     

X-ray diffraction and fracture based analysis of residual stresses in stainless steel–epoxy interfaces with electropolishing and acid etching substrate treatments

The aim of this study is to investigate the effect of a stainless steel surface condition on the thermal residual stresses at a bi-material interface. AISI 304 stainless steel–epoxy specimens with either as-received, nitric acid etched or electropolished substrates were prepared. Exact specimen curvatures and an analytical method were used to estimate residual stresses and the behaviour of the epoxy layer. X-ray diffraction stress measurement (XRD) was performed to determine the interfacial stress state. In addition, a method was developed to examine the interface fracture toughness of the specimens. Based on the results, the residual stress estimation at the interface was confirmed and the effect of the surface treatments on the interface fracture toughness was evaluated.     

Equilibrium morphology of gas–liquid Janus droplets: A numerical analysis of buoyancy effect

In this article, a theoretical model for predicting the equilibrium morphology of gas–liquid Janus droplets was built. Based on this model, the effects of bubble radius and volume ratio on morphology change was systematically studied. The increase of bubble radius causes the two parts (bubble and oil drop) in Janus droplets tend to merge while the impact of volume ratio is complicated. When volume ratio increases, these two parts firstly tend to merge, then gradually separate. The accuracy of this model was verified by experimental results.     

Adsorption of Cd and Cr ions from industrial wastewater using Ca doped Ni–Zn nanoferrites: Synthesis,characterization and isotherm analysis

Removal of heavy metals (Cd and Cr) from industrial wastewater by adsorption onto a series of Ca substituted nickel zinc nanoferrites (Ca_xNi_0.4Zn_0.6-xFe₂O₄ (x = 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6)) (CNZNFs) was studied in detail. The effect of calcium doping and contact time over adsorption of cadmium and chromium ions was investigated and maximum uptake of Cd (98.25%) and Cr (51%) ions were marked by prepared nanoadsorbents. Structural studies confirmed the formation of spinel structured nanoparticles with crystallite size ranging from 24 to 38 nm while porosity was observed to vary from 52% to 58% with calcium concentration. Pseudo second order (PSO) kinetic model for adsorption of both heavy metals (cadmium and chromium) was observed to be better fitted with adsorption data. Maximum adsorption efficiencies for Cd (128.20 mg/g) and Cr (23.54 mg/g) were found by the data fit of Langmuir isotherm model. Additionally, the adsorption data was found to obey Langmuir isotherm model for both heavy metals due to higher values of correlation coefficients (R² = 0.94131 for cadmium and 0.91091 for chromium) than Freundlich isotherm model (R² = 0.5865 for cadmium and 0.4599 for chromium).     

A comparison of conventional and optimized thermally coupled reactors for Fischer–Tropsch synthesis in GTL technology

In this research, the conditions at which a thermally coupled reactor – containing the Fischer–Tropsch synthesis reactions and the dehydrogenation of cyclohexane – operates have been optimized using differential evolution (DE) method. The proposed reactor is a heat exchanger reactor consists of two fixed bed of catalysts separated by the tube wall with the ability to transfer the produced heat from the exothermic side to the endothermic side. This system can perform the exothermic Fischer–Tropsch (F–T) reactions and the endothermic reaction of cyclohexane dehydrogenation to benzene simultaneously which can save energy and improve the reactions' thermal efficiency. The objective of the research is to optimize the operating conditions to maximize the gasoline (C₅⁺) production yield in the reactor's outlet as a desired product. The temperature distribution limit along the reactor to prevent the quick deactivation of the catalysts by sintering at both sides has been considered in the optimization process. The optimization results show a desirable progress compared with the conventional single stage reactor. Optimal inlet molar flow rate and inlet temperature of exothermic and endothermic sides and pressure of exothermic side have been calculated within the practicable range of temperature and pressure for both sides.